EP0348292B1 - Catalytic process for the dimerisation, codimerisation or oligomerisation of olefines using an autogeneous thermal regulation fluid - Google Patents

Description

The invention relates to a process for carrying out, generally under pressure, dimerization, codimerization and oligomerization reactions (in particular selective) of olefins, in the presence of at least one catalyst, usually solid, in at least one reaction zone. whose temperature is controlled by a heat exchange device based on hollow plates arranged within it.

Generally in this type of reaction, when operating according to the invention, at least one of the reagents is either in the liquid state, or in a state making it possible for its circulation by a pump (supercritical state), such as the ratio Tr between the temperature T (in kelvin) of the reagent system and the (pseudo-) critical temperature Tc (in kelvin) of said system is preferably less than 2, for example 1.5.

The olefin used can in particular be chosen from ethylene, propylene, styrene, one of the isomers of butenes or one of their mixtures. This olefin can be used in the pure state or as a mixture with one or more compounds which do not react on the catalyst under the conditions used, such as for example cyclic or acylic saturated hydrocarbons, in particular those having from 2 to 10 carbon atoms. The concentration of the olefin in the mixture can be from 5 to 100%, preferably from 10 to 100% by weight.

The invention relates more particularly to a process for the selective dimerization of propylene to 4-methyl-pentene-1, for example by means of solid catalysts based on potassium and / or sodium.

It is known to dimerize or oligomerize olefins in a homogeneous liquid phase to obtain, for example, C6 dimates (patents of the applicant US-A-4283305 and 4366087).

It is much more difficult to do the selective dimerization when using a heterogeneous catalyst, for example to dimerize propylene to 4-methyl-pentene-1, with sufficient selectivity, in particular greater than 85%. It is indeed necessary then to maintain within fairly narrow limits, a relatively constant temperature below which the activity of the catalyst falls to a value which makes the reaction unusable industrially and above which intervene consecutive reactions of isomerization which lower selectivity and lead to almost insurmountable separation problems.

The most frequently used isothermal reaction system is the single-pass shell and tube reactor where the interior of the tubes is filled with catalyst and thus constitutes the reaction medium. However, in selective dimerization, the catalytic system generally undergoes spontaneous and / or accidental deactivation (due to impurities), which requires the periodic renewal of this catalyst, a constraint which is technically difficult to implement with a reactor in which the number of tubes important must be filled and emptied one by one manually.

It is also known, when the temperature of the reaction must be kept within relatively narrow limits, to place within the catalytic bed a heat transfer device either based on tubes (GB-B2046618) or based on plates (US -A-3666423) or based on grids (US-A- 4693807), and to circulate inside this device a fluid intended for heat transfer and commonly known as thermoregulation fluid.

The drawback in the use of a tube-based heat transfer device comes from the fact that the connection between these individual tubes is very bulky and that, consequently, the assembly of the assembly is very difficult to carry out correctly. inside the reactor. The drawback of the plate-based heat transfer device of US-A-3666423 is its size and its low efficiency. To be able to withstand the reaction pressure, the plates are only partially hollowed out and the thermoregulation fluid thus has only a small part of the surface of the plates to do its exchange work.

In its patent US-A-4544544, the applicant has proposed, for gaseous reagent systems, a method allowing the use of hollow plates, made of thin sheets and of rectangular internal section.

The plates used in the methods according to the present invention work very little on the stress, which allows them to be completely hollowed out and to allow the thermoregulatory fluid to ensure the exchange through the entire available surface. In addition, the assembly and connections are simple enough to be carried out easily in the limited space offered by the reactor.

• - le fluide réactionnel va d'abord être employé comme fluide de thermorégulation de l'unité et du lit de catalyseur ; ensuite, il traversera le lit de catalyseur solide enfermé dans une enveloppe (1) de forme sensiblement cylindrique et allongée ;
• - le sein du lit catalytique est refroidi par le cheminement du fluide de thermorégulation qui circule dans un dispositif d'échange thermique plongé dans ledit lit catalytique et à base de plaques creuses fabriquées, parexemple, à partir de tôles minces plates ou ondulées comme il sera expliqué plus loin ;
• - le fluide de thermorégulation circulant à l'intérieur des plaques comprend le(s) réactif(s) constituant la charge fraîche, la circulation de ce fluide étant habituellement assurée par au moins une pompe (13) ;
• - le système de thermorégulation est un système ouvert sur le système réactionnel ; en effet, il est alimenté en continu par le(s) réactif(s) d'appoint qui passe(nt) directement du système de thermorégulation dans le réacteur sans barrière mécanique permanente ou transitoire.

The present invention uses a continuous single stage reaction system equipped with a heat transfer plate apparatus. Figure 3 explains how the unit works:

• - The reaction fluid will first be used as the thermoregulation fluid for the unit and the catalyst bed; then it will pass through the solid catalyst bed enclosed in an envelope (1) of substantially cylindrical and elongated shape;
• the breast of the catalytic bed is cooled by the path of the thermoregulatory fluid which circulates in a heat exchange device immersed in said catalytic bed and based on hollow plates manufactured, for example, from thin flat or corrugated sheets as it will be explained further;
• - the thermoregulation fluid circulating inside the plates comprises the reagent (s) cons titling the fresh charge, the circulation of this fluid usually being provided by at least one pump (13);
• - the thermoregulation system is a system open to the reaction system; in fact, it is continuously supplied by the auxiliary reagent (s) which passes directly from the thermoregulation system into the reactor without a permanent or transient mechanical barrier.

According to the process of the invention, the fresh charge (for example liquid propylene) is sent, under a pressure generally between 1.2 and 12 MPa, into the conduit 8 of the manufacturing unit (for example methyl- 4 pentene-1).

This fresh charge is first preferably indirectly preheated by hot reaction effluent (coming from line 5) through the heat exchanger 9. It then passes through line 10 and meets a fraction recycled from the thermoregulation fluid which will be called "recycled charge" thereafter, this recycled fraction being brought in through line 11.

The weight ratio between the recycled charge and the fresh charge is usefully between 1 and 500, preferably between 2 and 200, and even more preferably between 5 and 100.

The mixture thus obtained (fresh charge + recycled charge) forms the thermoregulation fluid (or heat transfer fluid) of the reactor (1). This fluid, which is generally between 100 and 200 ° C, preferably around 150 ° C, and at a reduced temperature of about 1.13, and in a state such that it can always be conveyed by a pump, enters via line 2 into the interior of the hollow cooling plates (6.3) arranged within the catalytic bed contained in the reactor (1).

The thermoregulation fluid absorbs the heat of reaction released as the synthesis product is formed (for example methyl-4 pentene-1 obtained by selective dimerization of propylene). This heat transfer fluid leaves the reactor (1) via line 3.

It is then separated into two portions. A first portion forms the charge to be treated which will circulate through the catalyst bed. This charge will hereinafter be called "make-up charge". It is sent to the reactor (1) via line 14. A second portion of the thermoregulation fluid withdrawn through line 3 will be recycled through line 11 into the heat exchange plates 6.3 (mixed with fresh charge coming from driving 10). This second portion of thermoregulation fluid is called "recycled charge".

The "recycled charge" passes through the conduit 12 where it is sucked by the pump 13 (preferably centrifugal) to be injected into the conduit 11 already mentioned.

According to the characteristics of the invention, the weight ratio between the recycled charge and the make-up charge is advantageously between 1 and 500, preferably between 2 and 200 and even more preferably between 5 and 100. A ratio too low prohibits satisfactory thermal control within the catalytic bed; too high a ratio requires a passage section such that the hollow plates become too thick and too bulky.

The "make-up charge", not taken up by the pump 13, passes through the conduit 14 through the exchanger 15 whose role is to readjust the temperature at the inlet level of the reactor 1. This make-up charge leaves the exchanger 15 via line 4 and then crosses the catalytic bed contained in the reactor 1. The resulting reaction effluent is discharged from said reactor via line 5 to preheat the fresh charge through the exchanger 9. From 9 , said effluent is usefully directed, via line 16, to a distillation and conditioning unit (not shown in the figure).

When it is a question of dimerizing propylene selectively to 4-methyl pentene 1, use is made, for example, of a catalyst based on alkaline carbonate preferably impregnated with metal of the same family.

Thanks to the good thermal control ensured by the plate refrigeration system, the conversion could be pushed very far without affecting the selectivity of the operation.

• - on introduit une charge fraîche liquide, contenant au moins une oléfine, en mélange avec une charge recyclée définie ci-dessous, dans lesdits espaces internes creux délimités par des parois, le rapport en poids entre la charge recyclée et la charge fraîche étant compris entre 1 et 500, le mélange charge fraîche-charge recyclée formant le fluide de thermorégulation ;
• - on soutire le fluide de thermorégulation desdits espaces internes et on sépare ce fluide en deux portions appelées ci-après charge recyclée et charge d'appoint, le rapport en poids entre ladite charge recyclée et ladite charge d'appoint étant compris entre 1 et 500 ;
• - on renvoie ladite charge recyclée vers lesdits espaces internes à titre de composant du fluide de thermorégulation ;
• - on envoie ladite charge d'appoint dans le lit de catalyseur ;
• - on soutire un effluent réactionnel du lit de catalyseur.

Thus, the subject of the invention is a catalytic process for dimerization or codimerization or for oligomerization of olefins usually carried out under pressure, in the presence of a solid catalyst, in a reaction zone defined by an enclosure of substantially cylindrical and whose section is substantially circular, said enclosure containing a generally fixed bed of catalyst in which is immersed a plurality of hollow internal spaces, in which a thermoregulation fluid circulates, under a pressure substantially equal to the pressure to which is subjected the reaction mixture, a process in which:

• - Introducing a fresh liquid charge, containing at least one olefin, mixed with a recycled charge defined below, in said hollow internal spaces delimited by walls, the weight ratio between the recycled charge and the fresh charge being between 1 and 500, the fresh charge-recycled charge mixture forming the thermoregulatory fluid;
• - the thermoregulation fluid is withdrawn from said internal spaces and this fluid is separated into two portions called hereinafter recycled charge and make-up charge, the weight ratio between said recycled charge and said make-up charge being between 1 and 500 ;
• - said recycled charge is returned to said internal spaces as a component of the fluid thermoregulation;
• - Said makeup charge is sent to the catalyst bed;
• - A reaction effluent is drawn off from the catalyst bed.

The invention also relates to the implementation of said method with the use of hollow internal spaces of particular design for the circulation of the thermoregulation fluid.

In Figure 1 the hollow internal spaces (or plates) have flat faces. FIGS. 2A, 2B, 2C and 2D represent plates according to an improvement of the invention.

• a) au moins un collecteur distributeur central (6.1), par exemple vertical, dont l'axe correspond généralement à l'axe de l'enceinte, qui est situé dans la partie supérieure de l'enceinte et est connecté à la conduite 2,
• b) une pluralité de collecteurs distributeurs (6.2), perpendiculaires à l'axe de l'enceinte, ces collecteurs étant connectés individuellement au collecteur distributeur central (6.1),
• c) au moins un collecteur receveur central (6.5), par exemple vertical, dont l'axe correspond en général à l'axe de l'enceinte, qui est situé dans la partie inférieure de l'enceinte et est connecté à la conduite 3,
• d) une pluralité de collecteurs receveurs (6.4), perpendiculaires à l'exe de l'enceinte, ces collecteurs étant connectés individuellement au collecteur receveur central (6.5),
• e) une pluralité de plaques creuses, continues et allongées destinées à la circulation du fluide de thermorégulation, chaque plaque comportant une ouverture sur un collecteur distributeur (6.2) et une ouverture sur un collecteur receveur (6.4).

In FIG. 1 is drawn an enclosure (1), of substantially cylindrical shape and the cross section of which has a substantially circular shape, comprising at least one pipe (2) for the introduction of a thermoregulation fluid, at least one line (3) for withdrawing said fluid, at least one line (4) for introducing a so-called make-up charge into the enclosure and at least one line (5) for withdrawing the reaction effluent from said enclosure. The enclosure (1) also contains:

• a) at least one central distributor manifold (6.1), for example vertical, whose axis generally corresponds to the axis of the enclosure, which is located in the upper part of the enclosure and is connected to line 2,
• b) a plurality of distributor manifolds (6.2), perpendicular to the axis of the enclosure, these collectors being individually connected to the central distributor manifold (6.1),
• c) at least one central receiving manifold (6.5), for example vertical, the axis of which generally corresponds to the axis of the enclosure, which is located in the lower part of the enclosure and is connected to the pipe 3 ,
• d) a plurality of receiver collectors (6.4), perpendicular to the exe of the enclosure, these collectors being connected individually to the central receiver collector (6.5),
• e) a plurality of hollow, continuous and elongated plates intended for the circulation of the thermoregulation fluid, each plate comprising an opening on a distributor manifold (6.2) and an opening on a receiver collector (6.4).

The faces of said hollow plates can be formed by corrugated sheets, the corrugations of which have one of the following shapes: square, rectangular, triangular, sinusoidal and chevron (see FIG. 2 D), the aim being to create strong turbulence on the flow of thermoregulation fluid.

Said hollow plates should be substantially parallelepipedic (6.3), each plate having two large parallel faces delimiting a plane arranged radially with respect to the axis of the enclosure and four thin faces, two of them being parallel to the axis, each plate being connected, by its upper thin face perpendicular to the axis of the enclosure, to a distribution manifold (6.2), and, by its lower thin face perpendicular to the axis of the enclosure, to a collector receiver (6.4). These four thin faces may possibly be non-planar, but for example semi-cylindrical.

It should be noted that adjacent channels can then be arranged in each of said substantially parallelepipedic hollow plates by means of corrugated sheets in order to improve the circulation of the thermoregulation fluid, the sections of said channels having either one of the following forms: square, rectangular (see Figure 2A), triangular (see Figure 2B), sinusoidal (see Figure 2C), these channels connecting together the two thin faces perpendicular to the axis of the enclosure of the same plate.

According to a variant of the invention, the hollow plates may possibly have different widths, which makes it possible to maintain a minimum ratio between the volume of the enclosure and the exchange surface, while avoiding too great a distance between a point any of the enclosure and the nearest plate.

The sheets optionally used in the various embodiments of the invention are generally less than 10 millimeters thick, preferably less than 3 millimeters thick.

In FIG. 1, given by way of example, the path of the thermoregulation fluid will be described through hollow plates (or hollow internal spaces) substantially parallelepidedic. The charge, in the form of make-up charge, enters the enclosure (1) via line 4, passes through the catalytic bed contained in said enclosure, then it exits from said enclosure, in the form of reaction effluent, by line 5. The autogenous thermoregulation fluid (that is to say constituted by one or more of the components constituting the fresh charge), passes from line 2 into the central distributor manifold (6.1). It is then distributed among the distributor manifolds (6.2). Then it enters each of the hollow plates (6.3) through their upper thin face perpendicular to the axis of the enclosure, these hollow plates being arranged within the catalytic bed contained in the enclosure (1). The fluid descends inside said hollow plates in the form of a sheet. At the outlet of the hollow plates, it is collected in the receiving manifolds (6.4) which are individually connected to the central receiving manifold (6.5) into which the fluid then passes. Finally, the thermoregulation fluid exits through the pipe (3).

The advantage of an autogenous thermoregulation fluid is, on the one hand, that there is no pressure difference between the inside and the outside of the plates (apart from that created by the pressure losses due circulation of the various fluids) and, secondly, that in the event of a leak, there is no danger of pollution of the system catalytic teme.

• - on envoie le fluide de thermorégulation, autogène (formé par le(s) composant(s) constituant la charge fraîche (et donc la charge recyclée», à travers une zone de distribution centrale (6.1),
• - on répartit ledit fluide en provenance de la zone de distribution centrale (6.1) dans des zones distributives (6.2),
• - on envoie ledit fluide, depuis lesdites zones distributives (6.2), dans lesdits espaces internes creux (6.3), délimités par des parois (lesdits espaces ayant une forme sensiblement parallélépipèdique), chaque espace (6.3) comportant alors deux faces larges parallèles délimitant un plan disposé radialement par rapport à l'axe de la zone de réaction (1) et quatre faces minces, deux d'entre ellles étant parallèles à l'axe de la zone de réaction (1), les deux autres étant perpendiculaires à cet axe), par leurface mince supérieure perpendiculaire à l'axe de la zone de réaction (1),
• - on fait circuler ledit fluide à l'intérieur desdits espaces internes creux (6.3) sous la forme d'une nappe,
• - on évacue ledit fluide de thermorégulation desdits espaces internes creux (6.3), par leur face mince inférieure perpendiculaire à l'axe de la zone de réaction (1), dans des zones collectrices (6.4) qui sont reliés à une zone de collecte centrale (6.5) par laquelle on soutire ensuite ledit fluide.

In short, in the improved invention:

• - the autogenous thermoregulation fluid (sent by the component (s) constituting the fresh charge (and therefore the recycled charge) is sent through a central distribution area (6.1),
• - distributing said fluid from the central distribution zone (6.1) in distributive zones (6.2),
• - Said fluid is sent from said distributive zones (6.2), into said hollow internal spaces (6.3), delimited by walls (said spaces having a substantially parallelepiped shape), each space (6.3) then comprising two wide parallel faces delimiting a plane arranged radially with respect to the axis of the reaction zone (1) and four thin faces, two of them being parallel to the axis of the reaction zone (1), the other two being perpendicular to this axis ), by their upper thin surface perpendicular to the axis of the reaction zone (1),
• - said fluid is circulated inside said hollow internal spaces (6.3) in the form of a sheet,
• - said thermoregulation fluid is discharged from said hollow internal spaces (6.3), by their lower thin face perpendicular to the axis of the reaction zone (1), in collecting zones (6.4) which are connected to a central collecting zone (6.5) by which said fluid is then drawn off.

In FIGS. 1 and 3, the enclosure (1) is shown in a substantially vertical position: the circulations of the thermoregulation fluid and the make-up charge can be done from top to bottom as described above, but also from bottom to top ( and therefore also against the current).

In addition, in FIGS. 1 and 3, the line 4 for admitting the charge (make-up) at the top of the enclosure 1 and the line 5 for withdrawing the reaction effluent at the base of enclosure 1, but these pipes (4 and 5) can in fact be located at any suitable level of the enclosure.

FIG. 1 represents an axial reactor in which the reactants cross the catalyst bed parallel to the axis of the reactor.

The invention can also be applied to a radial reactor comprising a permeable basket in the form of a cylindrical ring, for example delimited by two coaxial cylinders, in which the catalyst and the hollow plates are arranged and where the reactants pass through the bed perpendicular to the axis of the reactor.

FIGS. 2A, 2B and 2C show three substantially parallelepipedic hollow plates (6.3) in which adjacent channels (7a, 7b, and 7c) have been arranged by means of corrugated sheets, the sections of said channels having one of the shapes following: square, rectangular (7a), triangular (7b) and sinusoidal (7c), these channels connecting together the two thin faces perpendicular to the axis of the enclosure of the same plate: on the one hand, the presence of these adjacent channels ensures the solidity of the hollow plates (6.3) which can reach and exceed, by ten meters in height, on the other hand, it avoids the formation of dead zones which could form due to the flow in sheet of the thermoregulation fluid inside the plates.

The sheets can be assembled either by welding, or much more economically by soldering or by spots, or by immersion in a bath, or any other suitable technique.

The invention is illustrated by the following examples:

Example 1 (according to the invention)

In a vertical cylindrical reactor, 0.5 meters in diameter, equipped with a hollow plate thermoregulation system in accordance with FIGS. 1 and 2A, there is available the catalyst obtained by depositing 3.5% by weight of sodium on scales potassium carbonate bound by 1.5% graphite and previously activated at 230 ° C for 3 hours.

Then, under a pressure of 9 MPa, the unit shown according to FIG. 3 (via the conduit 8) is filled with propane and recirculation of 300 m ³ / h is ensured by means of the pump 13.

By means of the external steam heater 15 the propane temperature is gradually raised. When this temperature reaches approximately 150 ° C., propylene is introduced into the unit (via line 8), while purging the propane through line 16.

After a few hours, a steady state is established with a propylene flow rate of 5 m ³ / h, a propylene conversion of 28.3% and a selectivity to 4-methyl pentene 1 of 89.1%. This regime could be maintained for several hundred hours without significant variation in the conversion of propylene and the selectivity to 4-methul-1-pentene.

Example 2 (comparative)

The same catalyst is used as in Example 1, which is placed in the same reactor from which the thermoregulation system according to the invention has been removed, the hourly flow rate of propylene being identical.

The propylene reactor supply temperature is 130 ° C. The temperature of the reaction effluent at the outlet of the reactor is 190 ° C.

It is noted that the conversion of propylene does not exceed 15.0% and the selectivity to 4-methyl pentene 1 reaches only 65.1%, the major part of the by-products of the reaction being formed by 4-methyl pentene -2. We also note that after a fifty hours the catalyst has lost much of its activity.

Claims (6)

1. A catalytic method for dimerizing or codimeriz- ing or oligomerizing olefins, carried out under pressure, in the presence of a solid catalyst, in a reaction zone defined by a substantially cylindrical enclosure whose section is substantially circular, said enclosure containing a catalyst bed in which a plurality of hollow internal spaces having a substantially parallelepipedic shape is disposed, through which flows a thermoregulation fluid, at a pressure substantially equal to the pressure to which the reaction mixture is subjected, in which method :

- a fresh liquid charge , containing at least one olefin, mixed with a recycled charge defined below, is introduced into said hollow internal spaces defined by walls, the weight ratio between the recycled charge and the fresh charge being between 1 and 500, the fresh charge-recycled charge mixture forming the thermoregulation fluid;

- the thermoregulation fluid is drawn off from said internal spaces and this fluid is separated into two portions called hereafter recycled charge and make-up charge, the weight ratio between said recycled charge and said make-up charge being between 1 and 500;

- said recycled charge is fed into said internal spaces as thermoregulation fluid component;

- said make-up charge is fed into said catalyst bed;

- a reaction effluent is drawn off from said catalyst bed.

2. A method according to claim 1 wherein said fresh charge is preheated by indirect contact with the reaction effluent.

3. A method according to one of claims 1 and 2 wherein the weight ratio between said recycled charge and said fresh charge is between 2 and 200.

4. A method according to one of claims 1 to 3 wherein the weight ratio between said recycled charge and said make-up charge is between 2 and 200.

5. A method according to one of claims 1 to 4 wherein :

- the thermoregulation fluid is fed into a central distributing zone,

- the fluid from the central distributing zone is divided among distributing zones ,

- said fluid is fed,from said distributing zones,into said hollow internal spaces defined by walls, each hollow internal space having substantially a parallelepipedic shape, through their thin upper face perpendicular to the axis of said reaction zone,

- said fluid is caused to flow inside said hollow internal spaces in the form of a sheet,

- said thermoregulation fluid is discharged from said hollow internal spaces, through their lower thin face perpendicular to the axis of the reaction zone, into collecting zones which are connected to a central collecting zone through which said fluid is then drawn off.

6. A method according to one of claims 1 to 5 applied to the selective dimerization of propylene into methyl-4 pentene-1.

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